United States Patent
[111 3,979,285 [45] Sept. 7, 1976
[ 19]
Wegmiiller et al. .
PROCESS FOR THE PURIFICATION OF INDUSTRIAL EFFLUENTS [751 Inventors: Hans Wegmllller, Riehen; Jaroslav Haase, Basel, both of Switzerland
[54]
1731 Assignee: Ciba-Geigy Corporation, Ardsley, N .Y.
9/1946
Auten et al. ........... .., .......... .. 210/36
2,798,850
7/1957
Voightman et al.
2,955,067 3,398,092 3,699,039
10/1960 8/1968 10/1972
McBurrey et a1. ................ .. 210/502 Fields et a1. ..................... .. 210/24 Calmon et a1. .................. .. 210/28
3,716,483
2/1973
Renner
3,790,370
2/1974
Lalancette . . . . . . .
. .. . . . . . ....
. . . . . . . . ..
. . . . ._
3,829,380
8/1974
Oohara . . . . . . . . . . . .
. . . . . . . . ..
210/40
210/42
R
'
May 29, 1975 [22] Filed: [21] Appl. No.: 582,021
210/40
3,853,758
12/1974
Hurwitz et al.
3,857,823
12/1974
Ackermann ...................... ., 210/502
210/37 R
FOREIGN PATENTS OR APPLICATIONS
Related US. Application Data
[63]
2,407,599
847,028
Continuation of Ser_ No. 356,853, May 3, 1973,
9/1960
United Kingdom
abandoned.
Primary Examiner-Thomas G. Wyse Attorney, Agent, or Firm-Joseph G. Kolodny; Edward
Foreign Application Priority Data
[301
May 10, 1972
Switzerland ................... .. 007012/72
152]
US. Cl. .............................. .. 210/36; 210/37 R;
[51] [581
Int. Cl.2 ...................... .. C02B 1/60; C02C 5/08 Field of Search .............. .. 210/24, 28, 36, 37 R,
,
210/502
210/37 B, 40, 502, 506-508 0
[56]
References Cited UNITED STATES PATENTS ‘
2,040,818
5/1936
‘
, McC. Roberts; Prabodh I. Almaula
[5 7]
ABSTRACT
A novel process for purifying industrial ef?uents which comprises bringing said effluents into contact with cellulosic absorbent which has been pretreated with precipitants.
‘ s ‘
Badollet ................ .; .......... .. 210/506
'
6 Claims, No Drawings
3,979,285 1
2
a. The so-called stirring process, wherein the water to
be puri?ed is stirred with the pretreated cellulose
PROCESS FOR THE PURIFICATION OF INDUSTRIAL EFFLUENTS This is a continuation of application Ser. No. 5 356,853, ?led on May 3, 1973, now abandoned. The present invention relates to a process for the
material in a vessel and the cellulose material and water are then separated from one another.
b. The so-called flow bed process in which the pre
treated cellulose material is kept in the suspended
puri?cation of industrial ef?uents, especially for the decolourisation of waste liquors arising in the textile,
state by the counter-current ?ow of the liquor to be
puri?ed. c. The so-called ?ltration process wherein the liquor
paper and leather industry, which is characterised in 1 that the effluents are brought into contact with cellu
to be puri?ed is passed through pre-treated cellu
losic absorbent which has been pretreated with precipi
lose filter material. Of these three process variants, the ?ltration process (c) is preferably used, and above all the following three
tants. Preferably, ?lters of cellulose itself or of waste sheets from printing are used.
The puri?cation of industrial effluents is a problem
apparatus variants are suitable.
and proves extremely dif?cult particularly when the
l. The treatment apparatus, for example dyeing de vice, is ?rmly connected to the ?lter apparatus.
removal of water-soluble organic substances is con cerned.
2. The filter apparatus is movable and can be coupled to any treatment apparatus, as required. 3. The ef?uents originating from the treatment li
As part of this problem, the decolourisation and puri ?cation of ef?uents arising in the textile, paper and leather industry is an urgent requirement.
quors are combined in a suitable vessel and are
thereafter ?ltered conjointly. The puri?cation of the ef?uents is preferably carried
Various proposals have already been made for re
moving residues of dyestuffs and auxiliaries from indus trial ef?uents. Thus, for example, it has been provided that the residual liquors, including wash waters, are collected in collecting tanks and that the residues of dyestuffs and auxiliaries are precipitated therein by addition of suitable flocculating agents and separated out by sedimentation and filtration. However, these processes suffer from various disadvantages. Above all,
out at 10° to l50°C. However, it is preferably carried out just below the treatment temperature, that is to say at between 30° and 130°C depending on the treatmentv conditions. The puri?cation of the ef?uents can also take place under pressure, if appropriate. I The cellulose to be used as the carrier material in the puri?cation consists, for example, of bleached or un
the volumes of water to be treated are extremely large
bleached spruce sulphite cellulose, Kraft cellulose or waste sheets from printing, which are in a suitable
and sedimentation is frequently protracted. Surprisingly, it has now been found that a complete or at least very extensive puri?cation, including decolourisation, of industrial effluents is achieved if these are brought into contact with absorbents which
form. The waste sheets from printing are disintegrated on machines suitable for this purpose, for example on a
Hydrapulper. The cellulose can be in the form of gran ules, ?lter paper or paper pulp.
consist of cellulose pretreated with precipitants. The
Suitable precipitants are in principle compounds
process according to the invention is above all suitable
’ which are adsorptively bound by the cellulose and which at the same time exert a precipitating or retain
for the removal of anionic dyestuffs, optical brighten ers, dyeing auxiliaries and washing agents, and for the elimination of residues of tanning agent.
40
By means of the process according to the invention it
is not only possible extensively to free incompletely spent treatment liquors from the abovementioned sub stances but also satisfactorily to purify the correspond ing liquors which have been diluted with rinsing efflu
45
agents or tanning agents. In this respect, water-soluble basic aminoplasts such as formaldehyde-dicyandiamide condensation products have proved suitable. Advanta geous results are conveniently achieved with condensa
tion products of formaldehyde, dicyandiamide and
ents and which in most cases contain mixtures of dye
stuffs and washing agents. Because of its broad applicability, the present pro cess permits a saving of fresh water, through possible
ing action on the residual substances in question such
as, for example, dyestuffs, optical brighteners, washing
urea or ‘an alkylenepolyamine with 2 to 12, preferably with 2 to 8, carbon atoms, and 2 to 5 amino groups.
The alkylenepolyamines are, for example, tetrae
recirculation of residual liquors or waste liquors which
thylenepentamine, triethylenetetramine, tributylene tetramine, diethylenetriamine, hexamethylenediamine,
arise, such saving being demanded with ever increasing
ethylenediamine, propylenediamine or butylenedia
50
mine. urgency at the present time. Where residual liquors or waste liquors are spoken of Suitable basic aminoplasts are, above all, formal in the process according to the invention, the ef?uents 55 dehydedicyandiamide-ethylenediamine or formalde of the textile, paper and leather industry which arise in hyde-urea-dicyandiamide condensation products. Pre
connection with dyeing, washing and tanning processes
ferred products are obtained, for example, by conden
are above all concerned, regardless of the apparatus sation of 2 mols of formaldehyde with 1 mol of the employed. These liquors can originate, for example, in reaction product of 2 mols of dicyandiamide with 1 mol the case of a dyehouse, from the customary dyeing 60 of ethylenediamine, or the corresponding acid salt such apparatuses, such as are used for dyeing loose ?bre material, tops, yarn and woven fabrics or knitted fab
as the hydrochloride. Other products which are also preferred are manufactured by condensation of 1 mol
rics, and also from cleaning apparatuses, for example from an open-width washing machine. The ef?uents to be puri?ed are preferably brought
each of urea, dicyandiamide and formaldehyde in the
presence of acid such as hydrochloric acid. 65 Further products are obtained by condensation of 3 into contact in the undiluted state with cellulose mate to 4 mols of dicyandiamide with 7 mols of formalde
rial pretreated with precipitants. In principle, three
hyde and 1 mol of the tetrahydrochloride of triethyl
processes'are suitable for this purpose:
enetetramine.
3,979,285
3
However, precipitants of particular practical interest
acids and low polyalkylenepolyamines can also be used in the present invention. Suitable polyamide resins which can be used for the
are the polyamidopolyamines which are obtained by
reaction of polymerised, preferably dimerised to trim erised, fatty acids with polyamines, preferably in such a ratio that the resulting polyamide resin has an amine
manufacture of the ?lter materials which can be em
ployed according to the invention are described, for example, in British Patent Speci?cations Nos. 726,570, 810,348, 811,797, 847,028, 865,656 and 1,108,558, for example the compounds which are sold under the tradenames “Versamid 115”, “Versamid 125”, “Vera samid 140”, “Ancamid 400”, “Beckalide K 189”, “Casamid 167”, “Casamid 185M”, “Genamid 2000”,
value in the range of about 200 to 650 mg of potassium
hydroxide per gram of polyamide. As polyamines which can be used for the manufacture of polyamides it
is possible to employ aromatic polyamines or especially aliphatic polyamines which can also contain heterocy clic structures, such as imidazolines. Polymeric fatty
acids, whichare advantageously present in such poly
“Genamid 250”, “Synolide 960”, “Merginamide L
amides, are obtained by polymerisation of one or more
410” and “Wolfamid No. 4” (“Ancamide", “Becka
unsaturated longchain aliphatic or aromatic-aliphatic
lide”, “Casamid”, “Genamid”, “Synolide”, “Mergina
acids or their esters or other derivatives which can 15 mide”, “Versamid” and “Wolfamid” are trademarks).
easily be converted into the acid. Suitable examples of such polymeric fatty acids are described in British Pa tent Speci?cations Nos. 878,985 and 841,554. These polyaminoamides can be employed by them
Further precipitants are the polymers of an alkylenei mine with 2 to 4 carbon atoms which have a molecular
weight (MW) of 20,000 to 80,000, preferably 30,000 to 40,000. Suitable alkyleneimines are in particular
ethyleneimine, propyleneimine, 1,2-butyleneimine and
selves or in combination with the abovementioned
dicyandiamide condensation products.
2,3-butyleneimine. Of all the alkyleneimines, ethylenei
The polymeric unsaturated fatty acids used here are
mine is preferentially used.
advantageously aliphatic ethylenically unsaturated di
Precipitants which consist of two components are also suitable for the manufacture of ?lter material of
meric to trimeric fatty acids. Preferably, the polyam
ides from polyalkylenepolyamines and aliphatic ethyl
25
enically unsaturated dimeric to trimeric fatty acids,
particularly high performance. Such precipitants are manufactured in a simple manner by polymer precipi
which are derived from monocarboxylic acids with 16
‘tation in the presence or absence of cellulose. This
to 22 carbon atoms, are manufactured. These mono
polymer precipitation is preferably carried out by pre cipitating the abovementioned polymeric poly-cationic
carboxylic acids are fatty acids, with at least one and
preferably 2 to 5 ethylenically unsaturated bonds. Rep
30 precipitants in an aqueous medium by means of a poly
resentatives of this class of acids are, for example, oleic
anionic polymer. In this way, sparingly water-soluble
acid, hiragonic acid, elaeostearic acid, licanic acid, arachidonic acid, clupanodonic acid and especially
polymer associates are produced, which are absorbed on the surface of the cellulose which may have been
linoleic acid and linolenic acid. These fatty acids can be
present during the precipitation. If the polymer precipi
' obtained from natural oils wherein they occur, above 35 tation is carried out in the absence of cellulose, the
all, as glycerides.
resulting polymer associates are subsequently applied,
The dimeric to trimeric fatty acids are obtained in a
in a suitable form, to the cellulose.
known manner by dimerisation of monocarboxylic acids of the indicated type. The so-called dimeric fatty
Optionally substituted homopolymers or copolymers
of aliphatic a,B-ethylenically unsaturated carboxylic
acids always contain trimeric acids and a small amount 40 acids, advantageously in the form of their alkali metal of monomeric acids.
salts, especially of the sodium or potassium salts, or in the form of their ammonium salts, optionally mixed
.
Dimerised to trimerised linoleic or linolenic acids are
particularly suitable. The technical products of these
with corresponding free polycarboxylic acids, have
acids as a rule contain 75 to 95 percent by weight of
above all proved suitable as poly-anionic polymeric
dimeric acid, 4 to 22 percent by weight of trimeric acid 45 precipitants. and 1 to 3% of monomeric acid. Accordingly, the Preferably, water-soluble optionally substituted molar ratio of dimeric to trimeric acid is about 5:1 to homopolymeric acrylic acids are used, for example 36:1. Polymeric fatty acids or esters which are used for homopolymers of the following monomers: acrylic the manufacture of the reactive polyamides can also be acid, methacrylic acid, a-ethylacrylic acid, a-iso
epoxidised, for example by reaction with peracetic
acid, performic acid or hydrogen peroxide and formic acid or acetic acid. Suitable epoxidised fatty acids and
50
propylacrylic acid, a-butylacrylic acid and a-chloroa crylic acid. Water-soluble homopolymers of acrylic or
esters are described in British Patent Speci?cations
methacrylic acid with a molecular weight of 20,000 to 1,000,000, especially with a molecular weight of
Nos. 810,348 and 811,797.
50,000 to 150,000, are particularly preferred.
Polyamides which can be used according to the in vention can also be condensation products of poly
meric fatty acids with polyamines, as described in Brit ish Patent Speci?cations Nos. 726,570 and 847,028, it being possible to react these products with epoxide resins which are produced by reaction of polyhydric
phenols with polyfunctional halogenohydrins and/or glycerinedichlorhydrin and which are described in US.
Pat. Nos. 2,585,115 and 2,589,245. Reactive forms of polyamides obtained by condensa
Copolymeric aliphatic a,B-ethylenically unsaturated carboxylic acids are above all copolymerisation prod ucts of acrylic acid and methacrylic acid, but also copolymerisation products of acrylic acid or meth acrylic acid with another substituted acrylic acid men 60 tioned earlier.
Further poly-anionic copolymerisation products are obtained by copolymerisation of acrylic or methacrylic acid with compounds containing vinyl groups and capa~ ble of copolymerisation, especially with water~soluble
tion polymerisation, at high temperatures, from a reac 65 or water-insoluble comonomers. As examples of water tion mixture which contains polymeric fatty acids soluble comonomers there may be mentioned: (manufactured according to British Patent Specifica a. comonomers containing sulphonic acid groups, tions Nos. 878,985 and 841,544), monomeric fatty such as styrenesulphonic acid;
3,979,285 ,
5 b. comonomers containing carboxylic acid groups, vsuch as crotonic acid; c. comonomers containing carboxylic acid amide groups, and their N-hydroxyalkyl derivatives, such as acrylic acid amide, methacrylic acid amide, N
nesium sulphate, magnesium chloride and calcium chloride has proved appropriate. Preferably, these
hydroxymethyl-, N-B-hydroxyethyl-, N-y-hydroxy
bases to theaqueous solution of the abovementioned
propyl- and N,N-bis-B-hydroxyethyl-acrylic acid amide, and N-hydroxymethyl-, N-B-hydroxyethyl-, N-y-hydroxypropyl- and N,N-bis-B-hydroxyethyl
metal salts. As inorganic bases, alkali metal hydroxides arev preferably employed, for example sodium hydrox ide, potassium hydroxide and aqueous ammonia, whilst
methacrylic acid amide;
as organic ‘bases alkylamines are above all employed, ‘such as, for example, methylamine, dimethylamine or
metal salts are employed in the hydrated form of the corresponding neutral or basic metal oxides. This is
appropriately done by adding inorganic or organic
-
d. water-soluble, especially sulphonated, derivatives ' of B-hydroxyalkyl-acrylic acid amides or -meth
trimethylamine, ethylamine, diethylamine or triethyl
acrylic acid amides which are obtained, for exam- ' ‘
amine and alkanolamines such as monoethanolamine,
ple, by condensation of acrylic acid halides or
diethanolamine or triethanolamine.
methacrylic acid halides, especially chlorides, with
The amount of themetal salts employed advanta geously varies between 10 and 300% relative to the
reaction products of alkanolamines and chlorosul—
phonic acid; e. copolymerisable aldehydes, such as acrolein or
7 amount of the precipitant employed. Preferably, 50 to 200% of the metal salt are used, relative to the used
crotonaldehyde.
amount of the precipitant employed. The pretreatment of the cellulosic material with pre
As examples of suitable water-insoluble comonomers 20
cipitants is appropriately carried out in aqueous sus
there may be mentioned; i. acrylic acid alkyl esters or methacrylic acid alkyl
pension, for example at room temperature, at 20°C. I However, it can also be carried out at an elevated tem
esters with l to 12 carbon atoms in the alkyl radi
perature, up to 100°C. The amount of precipitant em cal, which can optionally be substituted further, especially by hydroxyl groups, such as acrylic acid 25 ployed advantageously varies between 0.5 and 20% relative to the cellulosic material. Appropriately, 2 — or methacrylic acid methyl esters, ethyl esters,
B-hydroxyethyl esters, n-butyl esters and .dodecyl esters;
10% are employed for this purpose. As preparation for the pretreatment, the cellulose or . waste sheets from printing are converted into a form
'
. vinyl esters of aliphatic carboxylic acids possessing
1 to 12 carbon atoms or of mixtures of such car 30 suitable for this purpose, especially into a ?bre suspen
sion. Depending on thetemperature conditions chosen,
boxylic acids such as vinyl acetate, vinyl formate, vinyl butyrate or vinyl esters of the carboxylic acid
the duration of the pretreatment can vary between a
few minutes and several hours. The pretreated cellu lose is subsequently converted into ?lters or ?lter mate the tradename VEOVA 911 (also-called f‘Versatic 35 rials according to known methods. Acid” vinyl ester).
mixture with 9 to 11 carbon atoms known under
iii. Vinyl benzenes, such as styrene, chlorostyrene and methylstyrene.
Dyestuffs which are removed from the effluents by ' the process according to the invention can be both
'
The poly-anionic polymers mentioned can be manu water-soluble and water-dispersible dyestuffs or optical brighteners. The processis preferentially suitable for factured in a manner which is in itself known, in aque ous solution or suspension, under the action of cata 40 the removal of water-soluble, especially anionic, dye
lysts, preferably radical-forming catalysts, such as hy
stuffs or optical brighteners. _
drogen peroxide, ammonium persulphate, potassium
In the case of water-soluble dyestuffs, dyestuffs
persulphate or organic peroxides, for example diben zoyl peroxide, or by using ammonium persulphate and sodium bisulphite. They are appropriately manufac
, which are retained particularly well are those which are
water-soluble because of the presence of acid groups, 45
tured at a temperature between 40° and 100°C. Carboxymethylated cellulose derivatives can be em
ployed as further poly-anionic precipitants. Carboxy methylcellulose, which as a rule is used in the form of its water-soluble alkali metal salts, such as the sodium 50
such as carboxylic acid groups, but especially sulphonic acid groups or acid sulphuric acid ester groups. They can be reactive or unreactive towards the ?bre material to be dyed and can furthermore belong to the most diverse categories, such as, for example, those of the
styryl, oxazine, formazane, quinophthalone, triphenyl
salt or potassium salt, is particularly suitable. Such
methane, xanthene, perinone, azomethine, nitro, ni
carboxymethylcellulose derivatives appropriately have
troso, acridone or phthalocyanine dyestuffs or espe cially the metallised, metal-free or metallisable mono azo or polyazo dyestuffs.
a degree of substitution (DS) of 0.4 to 2 carboxy methylcellulose salts with DS = 0.7 to 1.2 are pre
ferred. (The degree of substitution DS is de?ned ac 55 The retaining action is very particularly pronounced cording to Enc. of Polym. Sci. and Technol. volume 3, in the case'of the so-called direct dyestuffs. However, the retaining capacity is also considerable in the case of page 468). The amount of anionic precipitant em
metal complex dyestuffs.
ployed advantageously ?uctuates between 10 and 200%, relative to the cationic precipitant. Preferably, 20 to 100% of the poly-anionic agent are employed.
To manufacture ?lter material of particularly high performance which in addition to high retention, for
example for anionic dyestuffs and optical brighteners, also displays a very high retention capacity for anionic surface-active agent and tanning-agents, a combination of the abovementioned precipitants with salts of polyv alent metals such as, for example, aluminum sulphate, aluminum chloride, iron sulphate, iron chloride, mag
60
The process according to the invention is not only suitable for the decolourisation of residual liquors which arise in the dyeing of textiles, paper or leather but also performs valuable service when it is a matter of
removing residues of optical brighteners from washing liquors and bleaching liquors. Particularly favourable 65 results are obtained in those cases in which the optical
brightener to be eliminated is of anionic character. Examples of such brighteners are: 4,4'-bis
(acylamino)-stilbene-2,2'-disulphonic acids, 4,4’-bis(
3,979,285
7 triazinylamino)~stilbene-2,2'-disulphonic acids, 4,4’ bis-(azolyl)-stiIbene-2,2'-disulphonic acids, stilbyl naphthotriazoles, bis-(benzoxazol-Z-yl) derivatives,
small portions, over the course of about 2 hours and
monomethine-cyanines, 2,7-bis-(aroylamino)-dibenzo
whilst stirring, into a flask which is immersed in a heat
B. A mixture of 533 g of ethylenediamine dihydro chloride and 673 g of dicyandiamide is introduced in
thiophene-dioxide-3,6-disulphonic acids, 1,3-diaryl
ing bath at 250° — 255°C. An easily stirrable melt is
pyrazolines, styrylbenzoxazoles, bis-styrylaryl com pounds, bis-benzoxazolylaryls or oxadiazoles. A further advantage of the process according to the
thereby produced. The mixture is stirred for a further hour at an internal temperature of 250° — 255°C. Dur
ing introduction of the mixture and during subsequent stirring, ammonia is split off. Thereafter the internal temperature is loweredv to about 155°C, whereupon
invention is based on the fact that it permits elimination
of anionic surface-active agents and anionic dyeing auxiliaries from aqueous waste liquors, Such anionic
147 g of glacial acetic acid are allowed to run in over the course of about 5 minutes. The internal tempera, ture is lowered to about 1 15°C by further cooling and 107 g of paraformaldehyde are introduced over the course of about 15 minutes. The internal temperature is then allowed to drop to 100°C and 363 g of 37%
compounds are described in more detail in the book
"Tenside-Textilhilfsmittel-Waschrohstoffe” (“Deter gents-Textile Auxiliaries-Raw Materials for Washing Purposes”) by Dr. Kurt Linder (published by Wissen schaftliche Verlagsgesellschaft MBH Stuttgart 1964), volume 1; pages 561-835. Anionic compounds of the alkylarylsulphonic acid type are of particular practical
strength aqueous formaldehyde solution are added
interest. The retaining capacity is very particularly
heated for about 10 — 15 minutes in a boiling water
alkylarylsulphonic acid type, in which the alkyl part has
ens, 600 g of watér at about 90°C are allowed to run inv
over the course of about 5 minutes. The mixture is now
pronounced in the case of anionic compounds of the 20 bath, in the course of which the reaction mixture thick 10 to 14 carbon atoms.
and the batch'is heated further, for a total of 2 hours, in
The process according to the invention can also be of assistance in cases where the elimination of anionic
the boiling water bath. In the course thereof, a clear
solution is produced after about 20 minutes. The inter
synthetic tanning agents, especially tanning agents
25 nal temperature is lowered to about 50°C, the mixture
which carry one or more sulpho groups in the mole ‘ .cule, is concerned. Such compounds are well-known to ’ experts under the name “Syntane". A more detailed
reaction product is dried at 50° — 60°C under reduced
description of these compounds is to be found in “Ull ' manns Encyklopadie der technischen Chemie” (“Ull
is neutralised by adding sodium bicarbonate, and the pressure. An almost colourless, solid residue is ob tained, which gives a clear solution in boiling water. 30
Filter material
rnanns Encyclopaedia of industrial Chemistry”), vol ume 11; pages 595-598.‘
C. A'suspension of 10 kg of bleached spruce sulphite
,
cellulose in 300 kg of water is mixed with 2.5 kg of the aqueous solution of the dicyandiamide + urea + for
Bysuitable choice of the precipitant it is possible, according to the invention, to remove up to 100% of
the impurity from\the effluents. Retention effects of 35 maldehyde condensation products according to In more than 4 g of residual substance, that is to say dye
struction A, described above. The entire mass is stirred
stuff, optical brightener, auxiliary, washing agent or
for 21/2 hours at 30° - 40°C. Thereafter the pretreated
from the effluents can be dried in a simple manner and 50 thereafter be passed to an incinerator. A further advan
similar properties is obtained.
cellulose is ?ltered off and dried. The 10 kg of cellulose tanning agent, per 100 g of cellulose ?lter can thereby contain 170 g of the condensation product A bound b be achieved. In cases in which it does not prove possi 40 absorption. . ' ble to achieve complete decolourisation or removal of D. If the 10 kg of bleached spruce sulphite cellulose the residual substances by a single pass of the residual in instruction C are replaced by 10 kg of waste sheets liquor through the ?lter, it is advisable to repeat the from printing, in the form of a ?ne suspension, and the ?ltration process. > It is also possible to reduce the ?lter materials used to 45 pretreatment is carried out as described under C, with a product according to Instruction B, a ?lter material a minimum by the same measure (recirculation). which has similarly good properties is obtained. A particularly economical advantage of the process E. If, in Instruction C, the spruce sulphite cellulose is‘ according to the invention is that the pretreated cellu replaced by Kraft cellulose, a ?lter material which has lose ?lters after saturation with the residual substances tage may be considered to be the fact that waste sheets from printing, the use of which in most cases presents problems, are very suitable for use in the process ac
cording to the invention.
The examples which follow explain the invention without restricting it thereto. In the examples, percent ages are percentages by weight throughout.
55
F. If, in Instruction C, the 2.5 kg of the precipitant A are replaced by 1 kg of Versamid 140, a polyamide having an amine value of 350 to 400mg of KOI-I/g, an effective ?lter material is obtained. G. If, in instruction C, the precipitant A is replaced by a combination of 200 g of Versamid 140 with 200 g of FeCl_»,. 6H2O, a ?lter material which has very good properties is obtained.
'
H. A suspension of 10 kg of ‘bleached spruce sulphite
MANUFACTURING INSTRUCTIONS
cellulose in 100 kg of water is mixed with 800 g of 50%
Precipitant
strength polyethyleneimine (M.W. 30-40,000). The entire mass is kneaded mechanically for 20 minutes.
A. 34kg of dicyandiamide, 18 kg of urea and 5.5 kg of ammonium chloride in 75 kg of 30% strength hydro
This mixture is subsequently dried in a vacuum oven at
chloric acid are boiled for 6 hours under re?ux. There
I. A suspension of 10 kg of ?nely chopped waste sheets from printing in 300 kg of water is stirred with 1 kg of Versamid 140 for 3 hours at a temperature of 20°—25°C. After this time. the ?ne suspension is pressed
after, 80 kg of 37.4% strength aqueous formaldehyde solution are added and the whole is stirred for 6 hours at 75° - 85°C. After completion of the condensation, 10 kg of glacial acetic acid are added to the solution.
90°C.
65
‘
out to 30 kg. The ?lter cake is dried in a vacuum oven
3,979,285 10 If the same ?ltration is carried out using 10 kg of untreated cellulose, only 35% of the total dyestuff are
at 80°—90°C. The dry mass is comminuted and stirred into 300 kg of water. 5 l of a 10% strength AlCls solu tion are allowed to run in and after 20 minutes 2 l of
retained.
'
ammonia solution (25% strength) are added to the aqueous suspension. The mass is again pressed out to
'
EXAMPLE 2
400 l of an intensely orange-coloured residual liquor which still contain 40 g of the dyestuff of the formula
30 kg and dried in a vacuum oven at 90°C.
J. If, in Instruction H, the polyethyleneimine is re
S0 Na
S03Na S0 3 Na
3
vS0 3 Na
CH 3
placed by a combination of 800 g of 50% strength are ?ltered through 1 kg of spruce sulphite cellulose polyethyleneimine with 1,025 g of Al2(SO4)3. 181-120, a pretreated according to Instruction C. The ?ltrate ob further suitable ?lter is obtained. tained under these conditions is practically colourless. K. A suspension of 10 kg of bleached spruce sulphite 20 A similarly good result is obtained if instead of the cellulose in 500 kg of water is treated with 1 kg of pretreated spruce sulphite cellulose according to In Versamid 140. The suspension is stirred for 300 min struction C the same amount of Kraft cellulose, accord utes at 20°C. 33.5 I of a l% strength polymethacrylic
ing to Instruction E, treated in the same manner is
acid solution (M.W. 80-100,000) which has been ad
employed.
justed to pH = 6.1 with sodium hydroxide solution are 25 EXAMPLE 3 2,000 l of a blue-coloured residual liquor which still
stirred into this suspension over the course of 20 min utes. The mass is stirred for. an additional short period and 6.67 l of a 10% strength AlCl3 solution are added.
contains _100 g of dissolved dyestuff of the formula
Thereafter the pH value of this suspension is adjusted to 9.5 with a 10% strength ammonia solution, the whole is stirred for about 60 minutes, and the ?lter material is
pressed out to 30 kg. The ?lter material is used directly, in this moist state, for the puri?cation of the effluents. L. A suspension of 10 kg of bleached spruce sulphite cellulose in 500 kg of water is treated with 1 kg of Versamid 140. The suspension is stirred for 300 min
'0—-cu——0 - NH 2
. 35
.
/
(5)
so
3Naj
utes at 20°C. 67.0 I of a 1.5% strength solution of the
sodium salt of carboxymethylcellulose (D.S. approx. 0.8) were stirred into this suspension over the course of
NHIKNrINHZ
20 minutes. The mass is subsequently stirred for an 40 additional short period and pressed out on a ?lter to a
weight of approx. 30 kg. A readily usable ?lter material is obtained. M. The ?lter is manufactured in the same way as in
Instruction L, but 1 kg of Versamid 140 is replaced by 1 kg of polyethyleneimine (M.W. 30-40,000) and the 67.0 1 of a 1.5% strength carboxymethylcellulose solu tion are replaced by 67.0 1 of a ‘1% strength polymeth acrylic acid solution (M.W. 80—100,000). EXAMPLE 1 2,000 l of a residual liquor of dark blue colour, which still contains 200 g of the dyestuff of the formula
(1)
S03Na
C1
are ?ltered through 10 kg of cellulose treated accord 50 ing to Instruction C, at a temperature of 90° — 95°C. If
these conditions are observed, 80% of the dyestuff are retained. If this ?ltrate, containing 20% of the residual dyestuff, is ?ltered a second time through the '?lter
/ /l O11£03m‘ GTNDiIO?N ’ I N NH NaO S 3
C.
0
in the dissolved form are passed, at a temperature of 65 material which has already been used, a completely 95° — 98°C, through a ?lter manufactured according to decolourised ?ltrate is obtained. If the same ?ltration is Instruction C. The ?ltrate resulting under these condi carried out using cellulose which has not been pre tions is now colourless.
'
treated, the dyestuff retention is only 7%.
.
3,979,285
11 EXAMPLE 4 ~
'
1,000 l of a brown-coloured residual liquor which still contains 50 g of dyestuff of the formula
/ \ 4TH
'
N/
\
2,000 l of residual liquor which still contains 9.2 g of the optical brightener of the formula
,
(5)
/C\
N ,
_ ll
'
,
>
N.---- C\N/C-,—NH— ‘
u. éo
‘
‘
-
3'
,
v
v
l
0113 v/
—NII-~C\N&C——~N\
'
CH
so3 Na
“1 -
"
N
ll
‘CH-CH
'
g .
Y
>
Hy —@
N
l
HOCH2W2
EXAMPLE 5
C\
. /
CH3
12
i
Na 03s
CH
2
OH
2
are forced, at a temperature of 75° — 80°C, through a
2"
20 ?lter consisting of 10 kg of spruce sulphite cellulose
which has beforehand been treated according to In struction C. The resulting ?ltrate has been completely freed of the optical brightener.
(Lil
25
' ‘
If, in this example, the 10 kg of spruce sulphite cellu lose pretreated according to Instruction C are replaced by 10 kg of Kraft cellulose which is treated, according to‘ Instruction C, with a condensation product manufac tured according to Instruction B, a ?ltrate which has been completely freed of the optical brightener is again
i
2Na+ 30 obtained.
'
_'
‘
35
4°
EXAMPLE 6
1,000 l of a residual liquor' which still contains 8 g of --
'
,___J
l-IO
an optical brightener of the formula
3S \
S0311
'
,
(6)
NH
HN
l
l
/ C\ N/ N l II C C-NH
>
Q (HOCHZCHZ) 2NA,/ ‘
o
are passed, at a temperature of 85 C, through a ?lter
—-Cl-I=CH
/ C\ . N/ I ll ~NH-C
Q
SO3Na NaO 3 S
60
,
N (CH2CH?Ol-I) 2 '
‘
_
are passed, at a temperature of 35° - 40°C, through a
consisting of 5 kg of cellulose pretreated according to
?lter consisting of 5 kg of cellulose pretreated accord
Instruction C. The resulting ?ltrate proves to be largely colourless.
ing to Instruction C. The ?ltrate obtainable in this man ner has been completely freed of the abovementioned
If the cellulose pretreated according to Instruction C 6.5 1optical brightener, is replaced by the same amount of waste sheets from
printing, pretreated according to Instruction D, a
largely colourless ?ltrate is again obtained.
.
‘
EXAMPLE 7
2,500 l of a residual liquor of dark red colour, which,
37,979,285 13 '
- ’_ dyestuff of the formula coon
14
,
' has beenadjusted to pH 4 and contains 250 g of the
the dyestuff mentioned in Example 7-, in the dissolved form, are passed at a temperature of 95°—98°C through
" _' '
i
'
on
NH
30 3 Na inthe dissolved form, are passed, at a temperature of
a ?lter manufactured according to Instruction L. The
95°—98°, through’ a filter-‘manufactured according to ,
?ltrateresulting under these conditions. is practically
Instruction F.
.
I
colourless.
j
The ?ltrate resulting under these conditions is
now ‘
colourless.
15
-
EXAMPLE 8
_
,
EXAMPLE 13 7,500 l of a‘ residual liquor of dark red colour, which
3,400 l of a residual liquor of dark red colour, which
has been adjusted to pH 4 and which still contains 750 g of the dyestuff mentioned in Example 7, in the dis
has been adjusted to pH .4 and contains 340 g of the
20 solved form, are passed at a temperature of 95°—98°C
dyestuff of the formula
through a ?lter manufactured according to Instruction
'
3
. S03Na
1 NHOCe-Q
in the dissolved .form, are passed, at a temperature‘of 30 M. The ?ltrate resulting under these conditions is prac 95°—98°C, through a ?lter manufactured according to tically colourless. ., Instruction G. The ?ltrate resulting under these condi~ EXAMPLE [4 tions is practically colourless. If the same ?ltration is carried out using ?lter mate 8,500 l of rinsing liquor of dark red colour, which has rial described in Example 7, only 2,000 l'of the dyestuff 35 been adjusted to pH 4 with acetic acid and which con solution can be decolourised. tains 850 g of the dyestuff described in Example 7, and 1,940 g of an anionic auxiliary of the formula EXAMPLE 9
2,000 l of a residual liquor of dark red colour, which has been adjusted to pH 4 and which contains 200 g of 40
the dyestuff mentioned in Example 7, in the dissolved
0 H -C/N
17 35 \N
form, are passed at a temperature of 95°—98°C through a ?lter manufactured according to Instruction H. The
?ltrate resulting under these conditions is completely
CH;2
45
colourless.
3Na
EXAMPLE 10 4,600 l of a residual liquor of dark red colour which has been adjusted to pH 4 and which still contains 460
in the dissolved form are passed, at a temperature of 95°—98°C, through a ?lter manufactured according to g of the dyestuff described in Example 7, in the dis 50 Instruction K. The resulting ?ltrate is completely co lourless. solved form, are passed at a temperature of 95°—98°C through a ?lter manufactured according to Instruction EXAMPLE 15
J.
'
The ?ltrate resulting under these conditions is co lourless.
55
3,700 l of a dyeing liquor of dark blue colour which has been adjusted to pH 4 and which contains 370 g of the dyestuff of the formula
EXAMPLE 1 I 0
9,000 l of a residual liquor of darkred colour, which has been adjusted to pH 4 and which contains 900 g of
the dyestuff mentioned in Example 7, in the dissolved
H
60
form, are passed at a temperature of 95°—98°C through a ?lter manufactured according to Instruction K. The
NH- CH CH
.< 35,
’|
\
?ltrate resulting under these conditions is practically
O
colourless.
.,
Nll EXAMPLE l2
6,000 l of a residual liquor of dark red colour, which has been adjusted to pH 4 and which contains 600 g of
__
\ /
‘H5
65
503m. and 1,850 g of a dyeing auxiliary of the composition
16 factured according to instruction K, at a temperature
of 90°—95°C. The resulting ?ltrate is practically free of detergent. To test for the detergent, a 100 ml sample of the ?ltrate was adjusted to pH 4.5 with acetate buffer ’ and 5 ml of a 3% strength Al2(SO4)3.l8l-l2O solution
were added at room temperature. If the detergent is present, a turbidity or precipitate results. The ?ltrate‘
resulting from the experiment gave no precipitate with_ aliminium sulphate. We claim:
.
r
l. A process for purifying industrial effluents con
taining residual substances consisting of dyestuffs, opti cal brighteners, dyeing auxiliaries, detergents or tan ning agents, which comprises bringing said ef?uents into contact with a cellulosic adsorbent which is pre
treated with polyamidopolyamines produced by con densation from a polymeric fatty acid and a polyamine, to remove said substances. , .2. Processaccording to claim 1 wherein the puri?ca
"tion of the ef?u'ents is carried out at 30° to l30°C.
41.8% of water
3. Process according. to claim 1, wherein the ef?uents
‘in the dissolved form were passed through a ?lter man ufactured according to Instruction l, at a temperature of 95°—98°C. The resulting ?ltrate is colourless.
.
are passed over a cellulosic ?lter pretreated with said ' . polyamidopolyamines.
4., Process according to vclaim 3, wherein the cellu
25
losic ?lter is pretreated with a'polyamide which has an amine value in the range of 200 to 650 milligrams of ‘
EXAMPLE [6
1,500 l of a washing liquor which has been adjusted
potassium hydroxide per gram of polyamide. 5. Process according to. claim 3, wherein the cellu- l.
to pH 4 with acetic acid and which contains 1,500 g of a detergent of the formula
losic ?lter is pretreated with a mixture of said polyamidopolyamines and a salt of a polyvalent metal. 6. Process according to claim 5, wherein the cellu
‘losic'?lter is'pretreated with a mixture produced from said polyamidopolyamines and a salt of a polyvalent metal in the presence of an inorganic or organic base.
of commercial quality are passed through a ?lter manu
'
45
55
60
65
'
'
,*
i
*
*
*
*
